Photographic article of manufacture



00L 2, 1945. o w MURRAY 2,386,167

PHOTOGRAPHIC ARTICLE OF MANUFACTURE Filed Aug. 28, 1943 Gelatin Dye [ale/mediate.

lear Gelatin- Jz'lrcr Halide lag en Base.

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Gelatin Dye Inter/r2 edlatc. Barc- J'llver Halide Layer.

Gelatin Dye fmel'rlzealmtg.

I I I! Salve! Halide Layer.

claim far Receiving Inhibit/0n [magel2 1/ I I0 I I I I I I 4 1 I I III! Base. Gelatin Dye l/zzermedz'czae D h 5 Willard MU Pray INVENTOR.

BY r WW ATTORNEY Halide +0ye [ale/medals.

Patented Oct. 2, 1945 PHOTOGRAPHIC MANUFACTURE ARTICLE OF Otis Willard Murray, South River. N. J., assignor to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation oi Delaware Application August 28, 1943, Serial No. 500,346

11 Claima' (Cl. 95-2) This invention relates to photography. More particularly, it relates to methods for producing colored images and to novel elements therefor. Still more particularly, it relates to the production of dye image records in layersfree from reducible silver salts and to novel elements therefor, and to the preparation of such elements. The invention further relates to a method of making two and three or multicolor reflection prints and transparencies, especially paper prints.

This invention has for an object the provisions of a new method of making color prints. A further object is to provide a simple and economical method of making color prints. A further object is to provide a method of making a plurality of color prints from single image records. A still ftlrther object is to provide a method of making color prints free from silver images in situ therewith. Another object is to provide an element which can be used for the preparation of a two, three or multicolor print. A further object is to provide an element which can be used to produce a color print in toned and color developed images. Still other objects are to provide methods and elements for making color transparencies or reflection prints which require a minimum of equipment and processing steps and to make a general advance in the art.

The above objects are accomplished by the hereinafter described invention which in its broader aspects comprises producing- (l) A colored image record in an inner layer by exposing and color forming development or color tuning. and

(2) Producing a dye image color record in an outer layer of a color yielding element by contact development.

Colored image records can be produced in the inner layer by forming a latent image in the inner light sensitive silver salt layer and then coloring the developed image record. In color forming development procedures this can be accomplished in several ways-- (1) By having the two components necessary for forming color, e. g. the color former and the development agent in the developer solution (2) By using an immobile color former and having it uniformly distributed throughout the original light sensitive silver salt layer and a developer solution containing a color forming developing agent (3) By placing an immobile color developing agent in the original silver salt layer and using a solution containing a color former and other remaining necessary developer components (4) Placing both immobile color former and developer in the original light sensitive silver salt layer and using a solution containing the necessary developer components.

Toned images can be produced in the inner layer by printing a color separation record onto the light sensitive inner layer, developing and fixing, and then treating the silver image with a toning bath or baths.

The outer partial color record is produced in quinoneimine dyes including indophenol, indoaniline and indoamine dyes or azomethlne or azo dyes by imbibitlon contact with a separate photographic element bearing a. color record comprised of a reducible silver salt which is preferably a bleached silver image with the outer layer of a color yielding element containing a dye intermediate capable of forming the aforementioned dyes in the presence of a color forming developing solution. The respective color yielding elements and photographic elements contain. aqueous solutions of one or more developer components prior to contact with each other. The color element is preferably impregnated with an aqueous alkaline solution and the photographic element containing the reducible silver salt image is preferably treated with an aqueous solution of an aromatic amino color developing agent containing a color coupling developing agent prior to contact with the color element.

Various types of elements can be used in carrying out the above-described processes. In general, they comprise (a) A base (2:) One light sensitive silver salt layer on the In one modification, the color yielding layer is spaced from the silver salt layer by means of a water ermeable layer or suflicient thickness to prevent color coupling. In another modification, the developer oxidation products couple with dye intermediates in a separation layer which are chosen to form colorless or extremely weakly colored dyes. Suitable intermediates include 1- phenyl-4,6 diketotetrahydro pyridazine, perinaphthindone, etc. In still another embodiment an unstable color formingcgmpound which can be destroyed with weak acids, e. g. phenol, after processing, can be used in a separatory layer, e. g. of gelatin. In a preferred embodiment, however, the light sensitive silver salt layer and the color yielding layers are placed on opposite sides of the transparent water impermeable base.

The water permeable layers may be thin membranes or composed of water permeable materials, e. g. cellulose derivatives such as lower alkyl ethers and highly esteriiled partially hydrolyzed esters of cellulose, e. 8. methyl cellulose, ethyl cellulose, cellulose acetate, cellulose acetate propionate, regenerated cellulose, etc., or composed of him forming colloids, e. g. gelatin, agar-agar, polyglucuronic acid, deacetylated chitin, amino celiuloses, zein derivatives, polyvinyl alcohol. etc., which have been hardened it necessary so that they are cold water insoluble, but are water permeable.

The film base may be made of various mate rials, including cellulose derivatives, e. g. nitrocellulose, cellulose acetate, cellulose acetate propionate, synthetic resins, e. g. polyvinyl chloride, polyvinyl alcohol and polyvinyl acetal, and super polymers such as ethylene and isobutylene polymers and superpolyamines, e. g. nylon.

Color yielding layers of two general types constitute useful aspects of the invention. They may thus be (i) Composed of an immobile dye intermediate uniformly distributed. or dispersed in a water-permeable binding or supporting agent, and

(2) Composed of film forming synthetic resins containing nuclei capable of forming a quinoneimine or azomethine or azo dye on color forming development.

The aforementioned reversible colloids are useful binding agents.

In the accompanying drawing which will make the invention more easily understood, similar reference numerals reier to similar parts throughout the several views.

Fig. 1 is a schematic cross-sectional view of a film element useful for contact development and tuning or color development procedures.

Fig. 2 is a schematic cross-sectional view or a modified fllm element useful for contact development and toning or color development procedures.

Fig. 3 is a schematic cross-sectional view of a photographic element for contact development with an element similar to that of Fig. 2, but containing a color former in the silver salt layer.

Fig. 4 is a schematic cross-sectional view of a photographic element containing two radiation sensitive layers and a color yielding layer free from radiation sensitive materials.

Fig. 5 is a schematic cross-sectional view of a photographic element containing a gelatin layer, a silver halide dye intermediate layer and a color yielding layer free from radiation sensitive materials.

Referring now to the drawing. a base i which may be composed of a sized white paper or a cellulosic or resin material containing a white pigment is coated ilrst with a sub-stratum layer and then with a selatino-silver-halide emulsion a dye image by to term a layer 2. On layer 2 is coated In aqueous gelatin dispersion to form a clear separation layer I which is substantially thicker than layer 2. 0n layer I is coated a gelatin dispersion containing at least one immobile dye intermediate or color-former to form layer l. which layer yields the procedure described below or composite dye image. e gelatin dispersion I can be made by dissolving the dye intermediate in 5 to 10% caustic alkali to form a soluble paste. This may be diluted with about 5 parts of water and 1 part of alcohol, added to 6% aqueous gelatin and the excess alkali neutralized with a mineral acid such as hydrochloric. The concentration of the coating compositions, temperatures and coating speeds are adjusted to yield the desired thickness.

In Fig. 2. a subbed, transparent cellulose acetate film base I is coated on one side with a gelatin silver halide emulsion to form a thin layer 2'. 0n the other side of the base is coated a gelatin dispersion to form a layer 2' which contains at least one immobile color former so that said layer will yield a dye image or mixed dye images.

In Fig. 3 a thin transparent iilm base I, e. I. composed of a fusible superpolymer of the type set forth in U. 8. Patents 2,218,735 and 2,210,736, was coated on one side with an aqueous alkaline gelatin dispersion containing a blue-green immobile dyestufl component and a light sensitive silver halide, e. g.. silver bromide to form a thin layer 2' 0n the other side was coated thin layer 8" comprising an aqueous alkaline dispersion of gelatin containing a mixture oi immobile dyestuii' components yielding an orange-red dye, and a variable-gamma. mixed emulsion layeras described in U. 8. Patent 2,202,028.

Example I A color yielding element 0! the type shown in Fig. 1 having layer 4 composed ot gelatin containing 0.25 part of the o-sullobenzaldebyde dimer of I-(m-octadecoylaminophenyl) -3-methyl-fi-pyrazolone was exposed to a printing l lht passing through the red separation negative of a tri-pack color film combination. The color yielding element was then developed in a solution of the following composition:

. Parts 4-chioro-n-phenyi-phenol 2 N-diethyl-p-phenvlenediamine hydrochloride 2 NaaCOs 20 Sodium sulfite 1 H2O to 1000 N-diethyl-p-phenylene diamine hydrochloride "grams... l0 NaaSOa ..do 2 Metor' -do-- 0.0 Water to cc 1000 The bleached positive was then squeegeed in register contact with the color yielding element,

with the emulsion surface in contact with layer I and contact was maintained until a dye image iormed in layer 0. then removed. On this bluegreen magenta transparency is imbibed a yellow dye image from a matrix representing the minus blue record, thus giving a color print transparency.

Example II A color yielding element of the type shown in Fig. 1 containing as the blue-green color former in layer 4 a salioylaldehyde-o-suli'obenzaldehyde polyvinyl acetal was exposed to a printing light from "the blue-green record of bi-pack color separation negatives, developed, fixed and washed. The element was then treated in a toning bath or the following composition:

Uranium nitrate grams- Potassium oxalate "do"-.. 5 Potassium ierricyanide do 2 Ammonium alum -do 12 1161 (100 cc. conc./liter H20) cc..- Water to cm. 2000 was formed.

Example III A iilm element as shown in Fig. 3 was made by using as the color formers for layer I" a mixture of the reaction product of diacetoacettolidine sulione with ortho sulfobenzaldehyde and an ortho suli'obenzaldehyde dimer of i-(mstearoylaminophenyl) -3 methyl 5 pyrazoione and adding to layer 2", l-dodecoylamino-i'inaphthol. The element was exposed to a printing light from the orange-red record of bi-pack separation negatives. The color yielding element was then developed in a solution of the following composition:

N-diethyl-p-phenylene diamine hydrochloride grams 10 Sodium suliite -do- 2 Motel do 0.6 Water to liter 1 NasCOs --grams-- 30 iixed, washed, and soaked in 10% sodium carbonate. A positive from the blue-green bi-pack combination was bleached to form silver ferrocyanide images, washed, soaked in alkali solutionand squeegeed with the color yielding element after the manner set forth in Example I, yielding a color transparency having particularly good color rendition.

E's-ample IV A color yielding element oi the type shown in Fig. 2 containing layer I as a blue-green color former the arylide oi i-hydroxy-2-naphthoic acid with p-dodecylaniiide was exposed to printing light from an orange-red bi-pack color separation negative, developed and fixed. The

4o diates.

silver image record was then bleached by floating on a bath 0! the composition:

Potassium dichromate grams 2.25 Potassium bromide do 20 Copper sulfate do is Chrom alum ..-do- 3 Acetic acid cc 3.5 Water to liters 2 The element was bathed in hypo, washed and immersed in a dye bath containing 2.13 grams oi Wool Orange A (0.1. #151) of the formula and 1.54 grams of Berichrome Blue R. (C. I. of the iormula per liter of solution to form orange-red dye image; which were washed thoroughly. The layer on the opposite side of the support from that Example V A color yielding element of the type shown in Fig. 3 containing in layer 2 resorcinol-monooctsdecylether as a blue-green dye intermediate and in layer I" a mixture of the dye intermediates of Example 111 as orange-red dye interme- An orange-red color separation negative was printed onto layer 2" which was developed in an ordinary positive type metol-hydroquinone developer, fixed, washed, bleached with alkaline ferricyanide, washed and treated with a dyegenerating reducer such as bath "0 (hereinai'ter described) for 3 minutes, then bleached, fixed and washed. The blue-green color separation negative was printed onto a positive film stock which was developed and fixed and then bleached to silver ierrocyanide images, soaked in a 2% aqueous solution oi NaOH and the emulsion pressed into contact with layer 8" which had previously been soaked in an aqueous solution of the following formula:

Parts Monophenyihydrazine 2 2% aqueous sodium oleate 5 Sodium carbonate--- 2 The elements were squeegeed in register until a dye image formed in the outer layer, whereupon the elements were separated, washed and mounted on a paper base. A two-color print of good strength, color rendition and improved resistance to fading was obtained by the above combination or film element and process.

Example VI An element oi. the type set forth in Example IV was prepared which contains in addition to the dye intermediate in layer 3', p-amino-diethylaniline. The layer corresponding to I was processed after the manner set forth in Example IV except that all stages oi this process were conducted by floatation so as to exclude aqueous solutions from contact with layer I on the opposite side oi the support. A bleached positive was made in a similar manner to that described in Example IV and after soaking in an aqueous bath containing 30 cc. of hexamethylene diamine-Ld per liter, was placed in contact with the dry surface of layer 3 and allowed to remain until a color image appeared in said layer.

Example VI! A color yielding element of the type shown in Fig. 4 comprises a transparent support i coated on one side with an ordinary positive type silver bromide emulsion 5. On the other side the transparent support is a thin layer 6 of comminuted silver dispersed in gelatin so as to form a light barrier layer of metallic silver having a density such that less than 1% of the light is transmitted by the layer. On the light barrier layer is coated a silver halide emulsion layer 1. On the silver halide layer is coated a layer 8 of clear gelatin and over this a layer 0 of gelatin containing 25 parts of dlacetoacet-tolidine sulfom per 100 parts of gelatin. A positive type silver bromide emulsion coated on an aluminum foil support prepared as described in Mason 2,115,339 was printed from the blue separation negative, developed in an ordinary black and white developer, fixed, washed and bleached with alkaline ferricyanide. The green separation negative was printed onto the inner silver halide layer and, at the same time and in register, the red separation negative was printed onto the rear silver halide emulsion layer. The entire color yielding unit was then immersed in an ordinary black and white positive type of developer to develop the latent images in both of the exposed silver halide layers. Alter development, the film unit was washed. The inner silver image in layer I was then toned magenta by treating it first with a solution comprised of 1 liter of a solution containing nickel nitrate and 15% or potassium citrate with 50 cc. of a 4% solution of potassium ierricyanide and 5 cc. of nitric acid. The bleaching was done by floating the side of the film carrying the gelatin and dye intermediate and silver halide layers on the surface of the bleaching solution for approximately 6 minutes and then washing the entire film and then floating the same side in a solution comprising:

Parts by volume Saturated solution of dimethylglyoxime 50 0.4% sodium hydroxide 50 Water 400 after which the film was rinsed for two minutes. The rear side was then floated on an alkaline ferricyanide bleach bath, washed and redeveloped in a blue-green color forming developer similar to that described under Example I. Alter the final development, the blue-green layer was floated on an alkaline ferricyanide bleach bath, washed and the entire film was then immersed in a 5% plain hypo solution and given the final washing. After washing, the color element was immersed in a color developer as described under Example III and squeegeed into contact with the bleached positive image on the metallic toil base which had first been saturated with a 10% sodium carbonate solution, and left in contact until the yellow dye image was produced in the outer layer, after which it was given the final washing and Example V"! A color yielding element of the type shown in Fig. 5 comprises a transparent support i coated on the one side with a gelatin layer is containing approximately 1 gram of 2-hydroxy-3-methyl benzaldehyde phthalaldehydic acetal oi polyvinyl alcohol per 4 grams of gelatin. On the other side of the transparent support is coated a silver halide emulsion layer ll containing approximately 6 grams 0! l-(m-octadecoyi-aminophenyl-3-methyl-5-pyrazolone) per 1000 grams of emulsion. Over the magenta yielding layer is coated a layer 12 oi plain gelatin from an 8% aqueous dispersion. Using 3-color separation negatives, the green record was printed onto the silver halide layer and the entire him was then developed in a p amino N diethylaniline- "MetoP developer as described under Example I. The element was then treated with Farmer's reducer to remove the metallic silver and undeveloped silver halides from the inner layer. The red color separation negative was printed onto a positive silver halide emulsion on the aluminum oxide surface of aluminum foil prepared as described in Mason, U. 8. Patent 2,115,389. The red record positive was developed in an ordinary metol-hydroquinone developer, fixed, washed and bleached with alkaline ferricyanide solution. A positive matrix was prepared from the blue separation negative by printing through the base or a film coated with a positive type silver bromide emulsion, developing it in a pyro developer containing a minimum of sulflte (to harden the gelatin in situ with the silver image) fixing and washing in warm water to remove the unhardened gelatin. 01' course, any of the other well-known methods for forming matrices can also be used (for example, see "History of Three Color Photography," by E. J. Wall). The silver image was then removed by treatment with alkaline rerricyanide and sodium thiosuli'ate. A yellow imbibition image and a blue-green color developed dye image were then i'ormed respectively in the two outside layers oi this element in the following manner: The bleached positive from the red separation negative was satm'ated with 10% sodium carbonate solution and the bluegreen dye component layer was floated on a developer comprising:

p-Amlno-N-diethylaniline hydrochloride,

grams..- 10 NazSOa d0 2 Metol --do... 6 Water to liter 1 and then squeegeed into contact with the bleached image on the aluminum foil support. While this contact development was in progress, the upper clear gelatin layer was saturated with a 1% aqueous solution of silver nitrate and the matrix on the transparent base was soaked in a 10% potassium iodide solution and then squeegeed into registered contact with the clear gelatin layer forming therein a silver iodide image which is an excellent mordant for basic dyes. The matrix was then removed and a yellow dye fixed on the mordant image by floating on or swabbing on the surface with a solution oi Auramine (C. I. #655) or Chrysoidine (C. I. #20) in a 0.5% solution. Both foil matrix and the film positive squeegeed onto the two outer layers are then removed, the film is cleared in plain hypo, and washed, yielding a brilliant three color transparency comprisedot a metallo-organic image,

a,seo, 107

a color developed image and a mordanted dye mile- The invention is not limited to the exact procedures and materials, compounds or elements set. forth in the above examples. On the contrary, a wide variety of color yielding elements, dye components or color formers, developing agents and solutions, toning baths, dye mordants, coupling baths, can be substituted with similar results.

The color yielding elements may contain light sensitive layers composed of simple or mixed silver/halides which may contain the usual sensitineit, 1 stabilizers, fog inhibitors, emulsion hardeners. etc. Suitable types include silver chloride, silver bromide, silver chlorobromide, silver chlorlde-bromide-iodide, silver bromide-iodide, etc., which may contain cyanine, carbocyanine, polymethine cyanine, cyazine, carbocyaslne, pseudocyanine, krypt anine. merocyanlne, rhodanine, etc. salts and bases. The silver halide layers are anchored to the supports by means of the usual subbing solutions. Such solutions are also useful for anchoring dye component layers to bases.

While'the above description has been restricted for the most part to the formation of dye images i in non-photographic layers by bringing a separate element containing reducible silver salt images into contact with the dye yielding layer in the presence of the constituents of a color coupling developer, it is also possible to form such dye images by separate elements containing images other than silver salt images. For instance, one may employ the reducing action of chromium oxides formed by exposing bichromated gelatin layers. For preparing such images, a film support is coated with a thin gelatin layer, sensitised, for example, by bathing in an alkaline bichromate solution, dried and exposed under a negative to a printing light containing some ultra-violet radiations. The exposed film element is then soaked in alkali and pressed into contact with the color yielding element which has been saturated with a color coupling developing solution. In fact, each of the above described procedures for imbibition or contact development can be used with the elements containing other types of developable images.

general selected so that they together form a composite dye image which reproduces a color scene or object. Thus, the dye components used in the layer which is treated by contact development in general should form dyes complementary in color to that which exposed the color separation negative record employed therewith. Likewise, the dye components or color formers used in the inner layer or the developing solution used for processing thereof should form a dye which is complementary in color to that which exposed the color separation record. However, the above general considerations are not true when it is desirable to print a, negative color record from a negative color record or a positive color record from a positive color record. When reproduction eratum, a dye which forms any desired color can be used.

As examples of suitable yellow to orange-red color formers which can be used in emulsion layers or in developing solutions upon being dispersed therein if necessary by means of alkali and/or alcohol are the diacylacetamino-1,2,4,libenzobisthiazoles of U. 8. Patent 2,140,540 of which difuroylacetamino-l,2,4,5-benzobisthiazole and diacetoacetamino 1.2.43 benaobisthiazole are especially useful. Additional yellow color formers include 2-hydroxy-3-naphthoylaminobenzoyl-acetanilide, sodium stearoylaminobenzoyl-acetanilide-p-carboxylate, p-caproylamino, benzoyl-amino salicylic acid, furoylaoet-p-amino phenylamyl ether (described in Jennings and Middleton U. S. Patent 2,184,303, issued December 26, 1939, and di-picolinoylacet benzidine.

Suitable non-migratory magenta color formers which are especially useful are *1-(3'-sulfophenyl) 3 (4" stearoylaminophenyl) -3-(4"- dodecoylamino-phenyl) 5 pyrazolone, 4,4'-bis- (3 -methyl pyrazolonyll -diphenyl (described in Jennings and Middleton U. S. P. 2,200,924, issued May 14, 1940), 4,4'-methylene-bis-(mstearoylaminophenyl) -methyl pyrazolone (described in Jennings U. S. P. 2,294,909, issued September 8, 1942), and 4,4'-o-sulfobenzylidenebis (phenyl methyl pyrazolone) (described in 80 Jennings U. S. P. 2,294,909).

Suitable non-migratory blue-green color formers of especial utility include 4,4'-di-(l-hydroxy- Z-naphthoyl-amino) dlphenyl, l-hydroxy-2-carboxy-5-dodecoylamino naphthalene, l-N-steaa royl 4 N (1'-oxy-2'-naphthoyl) -phenylenedi- (described in McQueen U. S. P. 2,323,481, issued July 6, 1943), product of polyvinyl alcohol and salicyl-aldehyde (described in Borough and Mc- Queen U. S. P. 2,3 0,943, issued February 16, 1943).

Additional color formers which are useful not only with arylene diamino developing agents, but also the aryl-hydrazines, are described in U. S. Patents 2,154,918, 2,166,181, 2,178,612, 2,179,228, 2,179,238, 2,179,239, 2,213,986, 2,179,244, 2,186,045, 2,186,719, 2,186,734, 2,186,735, 2,186,736, 2,186,849, 2,140,540, 2,133,937, and 2,200,924, etc. Others are set forth in Sense and Murray application Serial No. 370,194, filed December 14, 1940, and may be substituted for the dye intermediates of the above examples in accordance with the teachings hereof.

The preferred developing agents which may be used in the dye coupling development steps here of are derivatives of p-phenylenediamine and particularly the asymmetric dialkyl p-phenylenediamines of l to 4 carbon atoms, e. g., p-amino dimethylaniline, p-aminodiethylaniline, p-aminodibutylaniline, etc. Other developing agents which may be used include p-phenylenedlamine itself, p-methylaminoaniline, p-ethylaminoaniline, p-aminophenol, N,N-diethyl-o-phenylenediamine, chloro-p-phenylenediamine, 1,2,5-toluylenediamine, 2-amino-5-diethyl-amino-toluene, p-amino-N-phenylmorpholine, N-p-aminophenyl-piperidine, N-methyl-N-hydroxyethyl-p-phenylenediamine, N-butyl-N-hydroxyethyl-p-phenylene-diamlne, 2-amino-5-(N-butyl-N-hydroxyethyl) aminotoluene, beta-gamma-dihydroxypropyl-p-phenylenediamine, etc. These aromatic of an original color object field is not a desidamino developing agents in the form of their organlc or inorganic acid salts may be used in the preparation of the developing solutions. The salts are in general more stable than the tree bases. As examples of suitable salts, mention is methanol) on 20 made of the hydrochloride, sulfates. acetates, etc. .5 sodium sumte m 8mm 2 In addition to the developing a ents as sfcrewater to 'I 7" 1 described, the developing solutions may contain from about 3 to 30 parts of an organic nigriigeiiii 3 m K base having an association exponent of a eas 5.0 to about 11.40 including aliphatic amines, 1 I igfigt ggggfifiE 3 primary. secondary and tirtitary al wl monome cc 25 nd olyamines, cycioalip a c amines, am-. monium hydroxides, ammonia. N-heterocyclic fgf' z anhy *fi" amines, etc. per 1000 parts 01 801E110. Suitable u r V bases are described in the follo Solutions In place or the specific hydrazlnes set forth in which can be used as described above. The bases Example 1v may be substituted other hydrazmes can be used in water alone as described in Exsuch as or p-t ]y1-hydraz1ne mample V. phenylhydrazine, p-hydrazino-diphenyl, p-bro- BathA 2o mo-phenylhydrazine, chlorophenyl hydrazines,

chloronaphthyl hydrazines, bromonaphthylhyp'mno N methymme drazines, p-diphenylhydrazines, p,p-diphenyldi- Ammmum hydmxide' hydrazines alpha-Ila hthylh d azi beta,- sodm sulflte anhy grams 2 p y water to liter 1 naphthylhydrazines which may be employed in the form of their salts, e. g., hydrochloride, ace- Bath. B 25 tate, chloroacetate, sulfates, etc. The hydrazines may be solubilized by means of long chain alip'mnwemymnmni: ggj '"'i" sg' 2 phatic carboxylic acid salts and long chain alinefifithylenedmm B n i 15 phatic sulfonic acid salts as set forth in Kirby U. S. P. 2,220,929. sodium summ' my i 2 In the case of elements which contain film water to forming color formers as the outer layers, no admg ditional binding agents such as gelatin need be present. Color iormers of this type which are pAminwiethylanume 3 8 especially suitable are (l) polyvinyl acetals oi Ammonium hydroxide' cone so 5 aromatic aldehydes which are capable of react- Sodmm carbonate a 2 ing with diazo compounds and the oxidation water 1 products of photographic color developers. The

Bath D acetals are flormed frlom1 pollyviziyl 3100:0101 patrtially hydro yzed p0 yv ny es ers an aroma c P-Ammodlemylamlme 3 aldehydes which contain a-phenolic hydroxyl, fl-dlmethylmmmthylamme 20 amino, alkyl-, cycloalkyl-, or aryl-substituted 30mm Bum, 3 amino group including mixed groups 0: this type water 1 which are further characterized in that they have Bath E areactlve position, but not necessarily unoccupied position, ortho orpara to the mentioned groups or pino le 2 the aromatic aldehydes having an active methyl- Pip e 25 enegroup. Thepreparation of suitable compounds Sodium sulflte. why 2 01' this type is set forth in Borough and McQueen water to 1 U. s. P. 2,310,943; and (2) condensation prod- Bath F ucts oi phenols and naphthols or hydroxy aromatic carboxylic or sulfonic acids with diiunc- 2-amino-5-dlethy m 4 ----B 5 tional resin-forming reagents such as aldehydes 'lrime hyll Y and ketones, dimethylol derivatives of phenols, ide cc 20 amides and amines and equivalent compounds. Sodium sulflte. anhy "4 5 The preparation of suitable color formers of this Water an 1 type is described in McQueen U. s. P. 2,323.4:11. Bum G Various other toning baths and procedures may be substituted for the specific one set forth in 4:4-dlaminodiphenylamine "grams" 1: an Example 11. Additional ones include:

cc m glgz rif hii arams 2 Toning bath 4 (m!) Water in lifer 1 Potassium i'erricyanide "grams" 12.5 Uranium nitrate do 12.5 Bath Rose Bengal ..-do 0.013 1:4-djaminomphthalene -grams 3 Naphthol yellow 0--- 0.013 nimethyl yclohexylamine cc 3n Iodine sodium 811mm. my gram 3 Glacial acetic acid cc 12.5 w te t ]1f er 1 water tn Bath 1 Toning bath B (minus blue) l-dietnylamino-l-naphthylamine grams 5 Vanadium oxalate solution cc so p-mmethyla,mixmethylamine cc 20 Oxalic acid (set) cc so Sodium sulnte, anhy grams 5 Glycer m 50 Water to er" 1 76 Water to m- 1000 Bath J p-Amlnodibutylaniline grams Hexamethylenediamine (55% solution in For use mix solutions A and B and add water to make 4 liters.

A number of different bleaching procedures can be used for the elements which are used for contact development. Films or plates containing a positive or negative silver image can be bleached color prints.

to redevelopable silver salts, as for example, with potassium ferricyanide, copper chloride, or copper bromide in the presence of an oxidizing agent such as chromic acid, potassium ferricyanide in the presence of alkali carbonate or ammonia, etc.

In place of the sodium carbonate solutions may be used potassium carbonate, potassium hydroxide, lithium carbonate, and other aqueous solutions for soaking the bleached photographic elements. The concentrations may range somewhat depending on the pH of the particular agent, the bleaching agent used, the dye intermediate used and the concentration of the developing agent, and amount of sulflte present. In general, amounts or 2 to 15% are practical.

In making the above color yielding elements, the color formers may be made into a paste with alkali and brought into solution with water or alcohol and then mixed with an aqueous dispersion of a reversible colloid, e. g., gelatin, preferably containing a dispersing agent and coated onto a base having a substratum of the type suitable for anchoring silver halide layers. The same types of coating procedures used for silver halide emulsion layers have been found satisfactory. In the case of film forming color formers, the alkaline aqueous or alcoholic solutions may be cast in a similar manner.

For the production of color prints and transparencies from strip or continuous film, e. g., colored cine prints or transparencies, the dye images can be prepared in the same general manner as previously described. The color yielding should in general have the same shape as the photographic element. Intimate contact may be maintained between the color element and the bleached element by running the elements in intimatecontact after they have been suitably treated for color coupling through pressure rolls or down a belt until color coupling and the formation of dye images has been completed.

the case of single color elements, the sprockets and perforations insure against slipping with the resultant production of fuzzy dye image records.

It will be apparent from the above that this invention is of wide utility and has a number of decided advantages.

A major advantage resides in the fact that twocolor prints can be made in a simple and economical manner. A further advantage resides in the fact that a number of tedious steps are eliminated irom prior processes of making two A still further advantage resides in the fact that the color development of one layer can be conducted under ordinary illumination which permits accurate registration of color records to be made.

As many apparently widely different embodiments of this invention may be made without departing from the spirit and scope thereof it is to be understood that I do not limit myself to the specific embodiments herein except as defined by the appended claims.

This application is a continuation-in-part of application Serial No. 370,195, now United States Patent 2,369,171.

r I claim:

1. A photographic element consisting of a transparent base, a light sensitive silver halide layer imposed on said base, a water permeable layer of appreciable thickness imposed on said layer and a water-permeable layer embodying a color-former which is free from silver and silver salts imposed on the last mentioned layer, said second layer being of such thickness that no coupling co-action takes place between the silver halide layer and said color-former.

2. A photographic element consisting of a transparent base, a light sensitive silver halide The pressure rolls and belts are preferably provided with sprockets which fit into perforations in the color yielding elements and photographic elements to insure accurate registration or images if they are mounted in registration with other color component records, c. g., from color separation negatives. However, even in layer imposed on said base, a water permeable layer of appreciable thickness imposed on said layer and a water-permeable layer embodying an immobile color-former which is free from silver and silver salts imposed on the last mentioned layer, said second layer being of such thickness that no coupling co-action takes place between the silver halide layer and said color-former.

3. A photographic element consisting of a transparent base, a light sensitive silver halide layer imposed on one side of said base and on the other side of said base a water-permeable colloid layer embodying an immobile color-former which is free from silver and silver salts.

4. A photographic element consisting of a transparent base, a water-permeable colloid layer containing light-sensitive silver halides and an immobile color-former on one side of said base and on the other side of said base a water-permeable colloid layer embodying an immobile coloriormer of a diil'erent type which is free from silver and silver salts.

5. An element as set forth in claim 4 wherein said color-formers are capable of forming dyes taken from the group consisting of quinoneimine, asomethine and azo dyes.

6. An element as defined in claim 4 wherein blue-green color-formers are in one of said layers and orange-red in the other.

7. A photographic element consisting of a transparent base, a light sensitive silver halide layer on one side thereof and in order on the other side thereof a comminuted silver colloid layer, a silver halide color-former layer, a waterpermeable colloid layer free from developer responsive materials and a color yielding layer comprising essentially an immobile color-former which is free from silver and silver salts, said fourth layer being of such thickness that no coupling co-action takes place between said third layer and said tlfth layer.

8. A photographic element consisting of a transparent base, a water-permeable colloid layer on one side thereof embodying a. color-former which is free from silver and silver salts and on the other side thereof in order a water-permeable silver halide layer containing an immobile coloricrmer and a water-permeable colloid layer free from developer responsive materials taken from the group consisting oi dye intermediates and reducible silver salts.

9. A photographic element having a support and at least one light-sensitive silver halide layer, an outer-most water-permeable colloid layer free from silver and silver salts embodying a color former, said layer being physically separated from all silver halide layers by a layer which prevents CERTIFICATE OF- CORRECTION.

Patent No. 2,586,167.

color coupling co-action with any silver halide layer thereof.

10. A photographic element having s. support and at least one light-sensitive silver halide layer. an outer-most water-permeable colloid layer free from silver and silver salts embodying an immobile color former, said layer being physically separated from all silver halide layers by a layer which prevents color coupling coaction with any silver halide layer thereof.

11. A photographic element having a transparent support and at least one light-sensitive silver halide layer, an outer-most water-permeable colloid layer iree from silver and silver salts embodying an immobile color former, said layer being physically separated from all silver halide layers by a layer which prevents color coupling coaction with any silver halide layer thereof.

O'I'ISWIILARDMURRAY.

October 2, 1915.

OTIS WILLARD MURRAY.

It is hereby certifiefd that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 2, sec and column, line 52, for "ll-chloro-n-phenyl-phenol" read --l -chloro-o phenyl-pheno1-- and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office Signed and sealed this 29th day r January, A. D. 191 .6.

(Seal) Leslie Frazer First Assistant Commissioner of Patents.

which is free from silver and silver salts, said fourth layer being of such thickness that no coupling co-action takes place between said third layer and said tlfth layer.

8. A photographic element consisting of a transparent base, a water-permeable colloid layer on one side thereof embodying a. color-former which is free from silver and silver salts and on the other side thereof in order a water-permeable silver halide layer containing an immobile coloricrmer and a water-permeable colloid layer free from developer responsive materials taken from the group consisting oi dye intermediates and reducible silver salts.

9. A photographic element having a support and at least one light-sensitive silver halide layer, an outer-most water-permeable colloid layer free from silver and silver salts embodying a color former, said layer being physically separated from all silver halide layers by a layer which prevents CERTIFICATE OF- CORRECTION.

Patent No. 2,586,167.

color coupling co-action with any silver halide layer thereof.

10. A photographic element having s. support and at least one light-sensitive silver halide layer. an outer-most water-permeable colloid layer free from silver and silver salts embodying an immobile color former, said layer being physically separated from all silver halide layers by a layer which prevents color coupling coaction with any silver halide layer thereof.

11. A photographic element having a transparent support and at least one light-sensitive silver halide layer, an outer-most water-permeable colloid layer iree from silver and silver salts embodying an immobile color former, said layer being physically separated from all silver halide layers by a layer which prevents color coupling coaction with any silver halide layer thereof.

O'I'ISWIILARDMURRAY.

October 2, 1915.

OTIS WILLARD MURRAY.

It is hereby certifiefd that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 2, sec and column, line 52, for "ll-chloro-n-phenyl-phenol" read --l -chloro-o phenyl-pheno1-- and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office Signed and sealed this 29th day r January, A. D. 191 .6.

(Seal) Leslie Frazer First Assistant Commissioner of Patents. 

